Methods of controlling nematodes using 2-butyl-4,6-dinitro-phenol carboxylic esters

ABSTRACT

Nematodes and fungi in the soil may be controlled by 2-butyl4,6-dinitrophenols and their carboxylic or carbonate esters.

lUmted States Patent 1 1 3,728,458 Pianka [451 Apr. 17, 1973 METHODS OF CONTROLLING [56] References Cited NEMATODES USING 2-BUTYL-4,6-

DINITRO-PHENOL CARBOXYLIC UNITED STATES PATENTS ESTERS 2,384,306 9/1945 Hester et al. ..424/311 x Inventor: Max Pianka St- Albans, Scherer et al 11 X [73] Assignee: The Murphy Chemical Company FOREIGN PATENTS OR APPLICATIONS Limited, St. Albans, England 394948 2,1964 Japan [22] Filed: July 24, 1969 855,736 12/ 1960 Great Britain 999,876 7/1965 Great Britain [21] App]. No.: 844,638

Primary Emminr-Albert T. Meyers [30] Foreign Application Priority Data Assistant Examiner-Allen J. Robinson July 25, 1968 Great Britain ..35,589/68 Thmas 52 US. Cl. ..424/311, 424/248, 424/266, [571 ABSTRACT 424/312, 424/313 424/314 Nematodes and fungi in the soil may be controlled by [5 Int- Cl. ..A0ln 2 buty] 4 6 dinitrophen ls and their carboxylic or car. 58 1 Field 61 Search ..424/31 1, 312, 313, mate esters 424/314, 248, 266

8 Claim, No Drawings METHODS OF CONTROLLING NEMATODES USING 2-BUTYL-4,6-DlNITRO-PHENOL CARBOXYLIC ESTERS 2 chloroacetate, bromoacetate, iodoacetate, 2- or 3- chloropropionate, 2,2-dichlo ropropionate or 2- chlorobutyrate. R may also be the group R This invention relates to a method of treating soil for 5 where R is an alkyl group having not more than the control of pests, particularly nematodes and fungi carbon atoms e.g. methyl or 2-R -4,6-dinitrophenyl, and to compositions thereforeand n 0, or an integer from 1 to 6, e.g. l or 2.

Certain species of nematodes, for example, root knot Alternatively, R may be a group of the formula nematodes, do serious damage to agricultural and hor- OC0.0R where R is an alkyl, alkenyl or alkynyl ticultural crops by attacking and feeding on the roots 10 group containing up to 11 carbon atoms. thereof. Among the crops that may be effected are al- Although R may be any branched butyl group it is falfa, beans, cucumber, cotton, peas, potatoes, sugar preferablyatertiary butyl group. beet and wheat. It has now been found that a number of The compounds of formula 1 are suitably applied to substituted phenols and their derivatives are highly the soil at a rate of from 1.12 to 56 kg/ha. However, toxic to soil-living nematodes and may be used for their 15 good control of nematodes is often obtained at rates of control. from 2.24 to 1 1.2 kg/ha.

According to the invention, therefore, there is pro- The compounds may conveniently be formulated as vided a method of treating soil for the control of negr n 0r p w r c i ng n in r solid diluent matodes and/or fungi which comprises applying thereto such as Fuller's earth impregnated with tl etgggicant of an effective amount of a phenol or phenolic ester havformula Such formulations y 0011mm from One 10 ing the formula I: 50 wt percent of the toxicant, or more or less, and may be applied to the soil in any suitable manner. It will be No: understood that a more effective nematicidal action will generally result when the formulation is physically mixed with the topsoil, such as by harrowing. I Alternatively, the compounds of formula I may be NO: I applied to the soil as a drench that is, a solution or i hi h dispersion of the toxicant in a solvent or liquid diluent,

R is a hydroxyl group or a carboxylic ester or car- Suitably Water. Such drehches y P p y bonate ester group diluting with water a concentrate containing the toxi- R i ab n hed b t l group; d lt h f cant, an emulsifying agent and preferably an organic R is a hydroxyl group; or a cyclic or acylic, saturated Solvent Such as p I or unsaturated (ethylenic, acetylenic or aromatic), car- Accordingly, h ihvehhoh fufther Prowdes a boxylic ester or carbonate ester group which may b position for application to the soilfor the control of nesubstituted with one or more of the following submatodes and/or fuhgl'compnslhg a compound of stituents: halogen atoms, nitro groups, amino groups formula I and a camel dllueht- Substituted amino groups, hydroxyl groups, carboxy] It has further beenfound that compounds of formula groups carboalkoxy groups alkoxy groups and I may exert a useful fungicidal effect, especially when kylthio groups 40 appl ed to the soil at ratesof the orderof 5.6 56 kg/ha The carboxylic ester group may, for example, be an P f y agalhst the $011 fuhgl Pythlum 9? h aromatic ester group (e.g., six membered monocyclic) to"), Rhlzoctoma (e-gw cotton) and vemcllmm substituted if desired by nitro or alkyl groups, or a (cg-ion tomato)- heterocyclic ester group (e.g., six membered monocylcompounds of i fonmfla hh methods of ic) including oxygen, nitrogen or sulphur hetero-atoms. Prepanhg them are dlsclosed Brmsh Preferably the group R has not more than 11 carbon 999,876 855,736; and The compounds of atoms and is suitably a straight chain alkanoate group formula I not disclosed these Patents y be such as acetate, propionate, hexanoate, octanoate or preparhd y hhalhgous ihethodsnonanoate, or an alkenoate group having from three to The lhvehhoh 1S descnbad by y of Illustration y 18 carbon atoms, such as acrylate, crotonate, sorbate m the followmg Examplesor oleate. Alternatively, R may be a monoor poly- EXAMPLE 1 halogenated alkanoate or alkenoate group suitably hav- The following compounds of formula I were ing two-14, e.g., two-four, carbon atoms such as H prepared (Table l) in which R =tert. butyl.

TABLE I Analysis, percent Found Required .\I.P., R Description, solvent of crystallization degrees Molecular formula Br N Br N 6 n-Vnlcrnto (.renm prisms, ethanol CHIIQONZOE 8. 3*ClllOl'OIil'ODlOllilill White plates, propun-2-eL CigHi NzO Cl 8.5 telleptanoate White prisms, methnnnL. CUIIglNLOfi 7. 95 1):: cnnoutc Ethanol i (33 11 51206 7.1 Undecanonte Methanol. t. -l.! Cflll gN Or. 6. .l liromoacotnte. White prisms, ethanol .7 70-75 (liglluBrNzilr, 7. 8 lf)ll0il(:(l,lll(l lzlle yellow prisms, ethanol a 81. 83 (hglhglNgOn 6.1) l)iohloroncotul. White prisms, t. lil. 5-- (h lhzClgNgOa 8. 0 Q-bromopropionn White needles, prnpnn-Z-ol... 7 (mll lirN Ou 7. 5 Lil-dishloropropionatc. While prisms, light petrolenl 1()l-- (mll fil Nmfi 7. 7 3,2-(1ihrmnopropionate 1l)'- "Hum-mun. 6.2 2-t-hlor0ln1tyrntc (lm, 14llnCll I-( ;J 8.1 2-ln'omohutyratu l0. 7.. a t. 72 7 lllI]TBl'N2()i' 7.2 2,3-(11bromohutyrnte Whitev prlslns, nn-thnnol. m. (f llmlir N m lentit-noate. to Yellow oiL. a... 77.. (i lli5Ng0 8.75 ()leilli'u .7 ()l'zlllgeoil e at. 1.003. (ygllllNgOfi 5.6 8,!l-(libromo ntt Brown oiL. 1.5280 (grill lllilyNgUr. 24.1 Nicotinati- 0, (1mm colon (ll ,nn-l lli 113M132 tmll Nnn 8.7 4-morpl1olinolormnte Brown prisms (i llwN or 7.1)

Compounds of formula I in which R tert. butyl were evaluated for the control of root knot nematodes (Meliodogyna spp.) on cucumbers. The. compounds were applied by soil incorporation to a depth of l'l5 cm just before planting. v I

The effectiveness of each compound was assessed at application rates of 22.4, 11.2 and 5.6kg/ha and is indicated, inTable II below, on an arbitrary scale running from (100 percent control) to i (no control).

Compounds of formula I in which R is tert. butyl and R is a carbonate group were tested for activity against root knot nematodes (Meliodogyna spp) by the procedure of Example 1. The rates of application were 3.36, and 2.24 kg/ha and three replications were carried out at each rate of application. The effectiveness was assessed as in Example 1. The results are shown in Table III.

TABLE III Rating at R 3.36kg/ha 2.24kglha methyl carbonate allyl carbonate 2-chloroethyl carbonate 2-ethoxyethyl carbonate propargyl carbonate l-ethoxycarbonyl ethyl carbonate untreated control EXAMPLE 3 The nematode Panagrellus was cultured on an oatmeal medium. The nematodes, of all age groups, were suspended in water to form a concentrated suspension and 1 ml. of this suspension was added to an aqueous medium containing one of a number of compounds of formula I at a concentration of 500 ppm. This diluted suspension was then further diluted as required to give concentrations of toxicant of 300, 100 and 30 ppm.

After 48 hours, the dead and live nematodes were counted visually under a microscope (3 field X 80 magnification). The percentage control was then assessed, after allowing for natural mortality.

In the compounds used, R tert. butyl and R carboxylic ester, or hydrogen. The results are shown in TableIV.-. w

A test was also carried out using 2-sec.butyl-4,6- dinitrophenyl n-heptanoate; the percent-control'at 300, 1 00 and 30 ppm was 80, 50 and 0 percent respectively,

TABLE IV R 17 Control at (ppm) Acetate I00 80 40 Hexanoate 50 I0 Heptanoate I0 5' Octanoate 40 I5 Nonanoate I00 100 35 Undecanoate I00 I00 20 Chloroacetate I00 I00 I00 Bromoacetate I00 95 Iodoacetate I00 I00 70 2-Chloropropionate 100 90 70 3-Chloropropionate I00 100 100 Z-Bromo ropionate I00 I00 100 2,2-Dich oropropionate I00 I00 100 2.2-Dibromopropionate I00 100 70 2-Chlorobutyrate 100 I00 30 Z-Bromobutyrate 70 30 0 2,3-Dibromobutyrate 100 90 25 Isobutyrate 100 35 5 Acrylate I00 100 20 Crotonate I00 90 20 Pent4-enoate 90 40 9,l0-Dibromostearate 85 40 5 p-Nitrobenzoate 90 75 50 Nicotinoate I00 75 5 Hydroxyl I00 95 80 Z-tert-butyl-4,6-Dinitrophenyl oxalate I00 I00 60 EXAMPLE 4 Compounds of formula I in which R tert. butyl were tested for activity against stem nematodes (Ditylenchus dipsaci). The compounds were applied by soil incorporation just before planting seeds of the test plant, alfalfa. All tests were performed with three replications. The test plants were assessed for disease two weeks after planting, and the nematicidal activity of the compound being tested was related to the following scale:

5 complete control 4 slight disease 3 moderate disease 2 moderately severe disease 1 severe disease (no control) (5) plant dead The results are shown in Table V.

TABLE V Activity Rating at R 11.2kg/ha 5.6kg/ha 2.8kg/ha acetate I (-5) l 5 (5) l 5 2 l crotonate 5 4 5 4 (5 2 5 3 l iodoacetate (-5) (5) 5 5 (5) 5 2 Z-chloropropionate 5 3 2,2-dichloropropionate (-5) 5 2 (5) 5 1 methyl carbonate 5 1 l 5 l l 5 l l l-ethoxycarbonylethyl carbonate 5 l 5 5 5 5 5 5 l propargyl carbonate untreated control EXAMPLE Compounds of the formula I were tested for activity aganist root knot nematodes (Meliodogyna spp) and stem nematodes (Ditylenchus dipsaci).

The compounds were applied by soil incorporation just before planting seeds of the test plants (cucumber for root knot nematode, and alfalfa for stem nematode). The test plants were assessed for disease incidence two weeks after planting.

The effectiveness of each compound is indicated in Table VI on an arbitrary scale running from 5 (100 percent control) to 1 (No control of disease), while indicates that the plant died or was severly injured and a reading was not possible.

TABLE VI Ester of 2-tert. butyl- Activity Rating 4,6-dinitrophenol Root nematode Stem nematode 22.4 kg/ha 44.8 kg/ha Fumarates:

n-Pentyl 5 3 n-l-Iexyl 4 n-Octyl 5 S n-Undecyl 5 2-tert. butyl-4,6- 5 4 dinitrophenyl Succinates:

Ethyl 5 5 Adipates:

Ethyl 5 l 2-tert. butyl-4,6- 4 l dinitrophenyl EXAMPLE 6 Some of the compounds used in Example 1 were tested for activity against soil fungi at rates of 22.4, 1 1.2 and 5.6 kg/ha. The three fungi used were Pythium (on cotton), Rhizoctonia(on cotton) and Verticillium(on tomato). The results, shown in Table VII below, are expressed in terms of an arbitary scale on which 5 represents no disease, 4 slight disease, 3 moderate disease, 2 moderately severe disease and l severe disease.

TABLE VII Rhizoctonia Verticillium R Pythium spp. solani albo-atrum 22.4 ll.2 5.6 22.4 11.2 11.2 5.6 kg/ kgl kg/ kg/ kg/ kg] kg] ha ha ha ha ha ha ha acetate 5 4 2 2 3 3 n-butyrate 5 n-octanoate 5 4 acrylate 5 S S 3 3 l l methacrylate 4 3 chloroacetate 5 5 l 5 5 3 3-chloropropionate 5 5 3 5 5 5 l I claim:

1. A method for controlling the nematode population in agricultural soils which comprises contacting said nematodes with a nematicidally effective amount of a compound having the formula:

in which R is selected from the group consisting of a straight chain alkanoyloxy group having two-1 1 carbon atoms, a straight chain monoor dihalosubstituted alkanoyloxy group having two-14 carbon atoms, a straight chain alkenoyloxy group having threel8 carbon atoms, nicotinate, 4-morpholinoformate, pnitrobenzoate, R O.CO(CH ),,CO.O, and R O.CO.CH =CH.C0.0, wherein R is a straight chain alkyl group having one-l0 carbon atoms or 2-R -4,6-dinitrophenyl and n is selected from the group consisting of zero and integers from one-six; and R is a branched butyl group.

2. The method as claimed in claim 1 wherein R is selected from the group consisting of acetate, propionate, n-hexanoate, n-octanoate and nnonanoate.

3. The method as claimed in claim 1 wherein R is selected from the group consisting of acrylate, crotonate, sorbate and oleate.

4. The method as claimed in claim 1 wherein R is a monoor dihalosubstituted straight chain alkanoyloxy group having two to four carbon atoms.

5. The method as claimed in claim 4 wherein said monoor dihalosubstituted group is selected from the group consisting of chloroacetate, bromoacetate, iodoacetate, 2- and 3-chloro-propionate, 2,2- dichloropropionate and 2-chlorobutyrate.

6. The method as claimed in claim 1 wherein R is CH O.CO.CI-I =CII.C0.0.

7. The method as claimed in claim 1 wherein R is tert. butyl.

8. The method as claimed in claim 7 wherein said phenolic ester is 2-tert-butyl-4,6-dinitrophenyl acetate. 

2. The method as claimed in claim 1 wherein R1 is selected from the group consisting of acetate, propionate, n-hexanoate, n-octanoate and n-nonanoate.
 3. The method as claimed in claim 1 wherein R1 is selected from the group consisting of acrylate, crotonate, sorbate and oleate.
 4. The method as claimed in claim 1 wherein R1 is a mono- or dihalosubstituted straight chain alkanoyloxy group having two to four carbon atoms.
 5. The method as claimed in claim 4 wherein said mono- or dihalosubstituted group is selected from the group consisting of chloroacetate, bromoacetate, iodoacetate, 2- and 3-chloro-propionate, 2,2-dichloropropionate and 2-chlorobutyrate.
 6. The method as claimed in claim 1 wherein R1 is CH3O.CO.CH CH.CO.O.
 7. The method as claimed in claim 1 wherein R2 is tert. butyl.
 8. The method as claimed in claim 7 wherein said phenolic ester is 2-tert-butyl-4,6-dinitrophenyl acetate. 